Sinapinic acid is a widespread compound in vegetable material and is as such common in the human diet. Recently it has drawn attention because of its biological activities. Sinapinic acid can be synthesized from syringaldehyde via the Knoevenagel-Doebner condensation. However this reaction is limited by the formation of 4-vinylsyringol after a second decarboxylation. To gain more detailed information about this reaction and to improve control over the formation of sinapinic acid, the concentration time history of syringaldehyde and the reaction products of this reaction have been monitored over time at different reaction temperatures. The formation of 4-vinylsyringol was found to be inhibited by performing the reaction at temperature below 80°C. This allows the reaction to be optimized for the production of sinapinic acid, with an optimal yield of 78% after 2.5 hours at 70°C.
{"title":"Conversion of Syringaldehyde to Sinapinic Acid through Knoevenagel-Doebner Condensation","authors":"J. Schijndel, L. Canalle, J. Smid, Jan Meuldijk","doi":"10.4236/OJPC.2016.64010","DOIUrl":"https://doi.org/10.4236/OJPC.2016.64010","url":null,"abstract":"Sinapinic acid is a widespread compound in vegetable material and is as such common in the human diet. Recently it has drawn attention because of its biological activities. Sinapinic acid can be synthesized from syringaldehyde via the Knoevenagel-Doebner condensation. However this reaction is limited by the formation of 4-vinylsyringol after a second decarboxylation. To gain more detailed information about this reaction and to improve control over the formation of sinapinic acid, the concentration time history of syringaldehyde and the reaction products of this reaction have been monitored over time at different reaction temperatures. The formation of 4-vinylsyringol was found to be inhibited by performing the reaction at temperature below 80°C. This allows the reaction to be optimized for the production of sinapinic acid, with an optimal yield of 78% after 2.5 hours at 70°C.","PeriodicalId":59839,"journal":{"name":"物理化学期刊(英文)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70503210","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photochemical reactions of microcystin-LR, a toxic compound produced by some blue green algae, were investigated. Ultraviolet absorption of microcystin-LR was assessed. Time-dependent density functional theory (TDDFT) calculations indicated that absorption peak at 238 nm was mainly due to excitation of electrons from the linear chain structure Adda of microcystin-LR. Irradiation of microcystin-LR with UV light resulted in the reduction of the 238 nm absorption peak and the appearance of a new peak at 300 nm. Density functional theory (DFT) and TDDFT calculations with a model molecule suggested that this 300 nm peak was due to tricyclo-Adda microcystin-LR, an intermediate in photochemical reactions of microcystin-LR. Analysis of the rate of this photochemical reaction showed that it was a first order reaction.
{"title":"Photochemical Reactions of Microcystin-LR Following Irradiation with UV Light","authors":"Yoshihiro Mizukami","doi":"10.4236/OJPC.2016.64008","DOIUrl":"https://doi.org/10.4236/OJPC.2016.64008","url":null,"abstract":"Photochemical \u0000reactions of microcystin-LR, a toxic compound produced by some blue green \u0000algae, were investigated. Ultraviolet absorption of microcystin-LR was \u0000assessed. Time-dependent density functional theory (TDDFT) calculations \u0000indicated that absorption peak at 238 nm was mainly due to excitation of \u0000electrons from the linear chain structure Adda of \u0000microcystin-LR. Irradiation of microcystin-LR with UV light resulted in the \u0000reduction of the 238 nm absorption peak and the appearance of a new peak at 300 \u0000nm. Density functional theory (DFT) and TDDFT calculations with a model molecule \u0000suggested that this 300 nm peak was due to tricyclo-Adda microcystin-LR, \u0000an intermediate in photochemical reactions of microcystin-LR. Analysis of the \u0000rate of this photochemical reaction showed that it was a first order reaction.","PeriodicalId":59839,"journal":{"name":"物理化学期刊(英文)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70503432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
It is currently admitted that the intermolecular forces implicated in Gas Liquid Chromatography (GLC) can be expressed as a product of parameters (or descriptors) of solutes and of parameters of solvents. The present study is limited to those of solutes, and among them the three ones are involved in the Van der Waals forces, whereas the two ones involved in the hydrogen bonding are left aside at this stage. These three studied parameters, which we call δ, ω and e, respectively reflect the three types of Van der Waals forces: dispersion, orientation or polarity strictly speaking, and induction-polarizability. These parameters have been experimentally obtained in previous studies for 121 Volatile Organic Compounds (VOC) via an original Multiplicative Matrix Analysis (MMA) applied to a superabundant and accurate GLC data set. Then, also in previous studies, attempts have been made to predict these parameters via a Simplified Molecular Topology procedure (SMT). Because these last published results have been somewhat disappointing, a promising new strategy of prediction is developed and detailed in the present article.
{"title":"A Revisited Definition of the Three Solute Descriptors Related to the Van der Waals Forces in Solutions","authors":"P. Laffort","doi":"10.4236/OJPC.2016.64009","DOIUrl":"https://doi.org/10.4236/OJPC.2016.64009","url":null,"abstract":"It is currently admitted that the intermolecular forces implicated in Gas Liquid Chromatography (GLC) can be expressed as a product of parameters (or descriptors) of solutes and of parameters of solvents. The present study is limited to those of solutes, and among them the three ones are involved in the Van der Waals forces, whereas the two ones involved in the hydrogen bonding are left aside at this stage. These three studied parameters, which we call δ, ω and e, respectively reflect the three types of Van der Waals forces: dispersion, orientation or polarity strictly speaking, and induction-polarizability. These parameters have been experimentally obtained in previous studies for 121 Volatile Organic Compounds (VOC) via an original Multiplicative Matrix Analysis (MMA) applied to a superabundant and accurate GLC data set. Then, also in previous studies, attempts have been made to predict these parameters via a Simplified Molecular Topology procedure (SMT). Because these last published results have been somewhat disappointing, a promising new strategy of prediction is developed and detailed in the present article.","PeriodicalId":59839,"journal":{"name":"物理化学期刊(英文)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70503148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Building on the recent success of the even-odd rule, the present paper explores its implications by studying the very specific case of OXO compounds. These compounds are usually represented with double bonds linking two oxygen atoms to a central atom—as in carbon dioxyde—yet can sometimes be drawn in a triangular structure, such as in calcium dioxyde. Measurement data moreover indicate that most OXO compounds have an angle around 120° between oxygen atoms, although that seems incompatible with triangular representations. The aim here is to unify these commonly admitted representations by linking oxygen atoms through a single bond that is longer than usual covalent bonds: an “elongated bond”. This elongated bond has the interesting effect of suppressing the need for double bonds between oxygen and the central atom. The elongated bond concept is applied to about a hundred of molecules and ions and methodically compared to classical representations. It is shown that this new representation, associated to the even-odd rule, is compatible with all studied compounds and can be used in place of their classical drawings. Its usage greatly simplifies complex concepts like resonance and separated charges in gases. Elongated bonds are also shown to be practicable with the isoelectronic rule as well as isomers, and throughout chemical reactions. This study of an especially long and wide angle bond confirms the versatility of the even-odd rule: it is not limited to compounds with short covalent bonds and can include OO covalent bond lengths of more than 200 pm and with OXO angles above 90°.
{"title":"Introducing an Extended Covalent Bond between Oxygen Atoms with an OXO-Shape in Ions and Molecules: Compatibility with the Even-Odd and the Isoelectronicity Rules","authors":"G. Auvert, M. Auvert","doi":"10.4236/OJPC.2016.63007","DOIUrl":"https://doi.org/10.4236/OJPC.2016.63007","url":null,"abstract":"Building on the recent success of the even-odd rule, the present paper explores its implications by studying the very specific case of OXO compounds. These compounds are usually represented with double bonds linking two oxygen atoms to a central atom—as in carbon dioxyde—yet can sometimes be drawn in a triangular structure, such as in calcium dioxyde. Measurement data moreover indicate that most OXO compounds have an angle around 120° between oxygen atoms, although that seems incompatible with triangular representations. The aim here is to unify these commonly admitted representations by linking oxygen atoms through a single bond that is longer than usual covalent bonds: an “elongated bond”. This elongated bond has the interesting effect of suppressing the need for double bonds between oxygen and the central atom. The elongated bond concept is applied to about a hundred of molecules and ions and methodically compared to classical representations. It is shown that this new representation, associated to the even-odd rule, is compatible with all studied compounds and can be used in place of their classical drawings. Its usage greatly simplifies complex concepts like resonance and separated charges in gases. Elongated bonds are also shown to be practicable with the isoelectronic rule as well as isomers, and throughout chemical reactions. This study of an especially long and wide angle bond confirms the versatility of the even-odd rule: it is not limited to compounds with short covalent bonds and can include OO covalent bond lengths of more than 200 pm and with OXO angles above 90°.","PeriodicalId":59839,"journal":{"name":"物理化学期刊(英文)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70502986","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Corrosion inhibition of mild steel in 0.5 mol/L H2SO4 was investigated in the absence and presence of different concentrations of thiosemicarbazide. The inhibition efficiency of thiosemicarbazide was studied by electrochemical impedance methods, potentiodynamic polarization and scanning electron microscopy at different inhibitor concentrations. Inhibition efficiency, corrosion rate and surface coverage were evaluated at different concentrations of thiosemicarbazide. Electrochemical impedance plots indicated that the presence of the inhibitors increased the charge transfer resistance of the corrosion process, increasing the inhibition efficiency. Polarization curves showed that this compound acted as mixed type inhibitor. The results of the investigation showed that this compound had good inhibiting properties for mild steel corrosion in 0.5 M sulfuric acid. The adsorption isotherm studies showed that Thiosemicarbazide adsorbed chemisorbed and formed a stable surface complex on the mild steel surface. And Langmuir obeyed the adsorption isotherm. Scanning electron microscopy analysis shows that, the surface morphology of the polished mild steel in the presence of thiosemicarbazide as inhibitor is smoother surface as compared with polished mild steel specimen in the absence of inhibitor.
{"title":"Investigate the Corrosion Inhibition of Mild Steel in Sulfuric Acid Solution by Thiosemicarbazide","authors":"F. Mahgoub, S. Al-rashdi","doi":"10.4236/OJPC.2016.63006","DOIUrl":"https://doi.org/10.4236/OJPC.2016.63006","url":null,"abstract":"Corrosion inhibition of mild steel in 0.5 mol/L H2SO4 was investigated in the absence and presence of different concentrations of thiosemicarbazide. The inhibition efficiency of thiosemicarbazide was studied by electrochemical impedance methods, potentiodynamic polarization and scanning electron microscopy at different inhibitor concentrations. Inhibition efficiency, corrosion rate and surface coverage were evaluated at different concentrations of thiosemicarbazide. Electrochemical impedance plots indicated that the presence of the inhibitors increased the charge transfer resistance of the corrosion process, increasing the inhibition efficiency. Polarization curves showed that this compound acted as mixed type inhibitor. The results of the investigation showed that this compound had good inhibiting properties for mild steel corrosion in 0.5 M sulfuric acid. The adsorption isotherm studies showed that Thiosemicarbazide adsorbed chemisorbed and formed a stable surface complex on the mild steel surface. And Langmuir obeyed the adsorption isotherm. Scanning electron microscopy analysis shows that, the surface morphology of the polished mild steel in the presence of thiosemicarbazide as inhibitor is smoother surface as compared with polished mild steel specimen in the absence of inhibitor.","PeriodicalId":59839,"journal":{"name":"物理化学期刊(英文)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70502858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photoacoustic spectroscopy was used to test the photoacoustic properties of sulfur hexafluoride, an optically thick and potent greenhouse gas. While exploring the photoacoustic effect of sulfur hexafluoride, the effects of the position of the microphone within a gas cell were determined. Using a 35 cm gas cell, microphones were positioned at 17.5 cm, the middle of the gas cell, 12.5 cm, 7.5 cm, and 2.5 cm from the window of the cell. From the photoacoustic signal produced for each resonance frequency at each microphone position, the effects of acoustic pressure produced at each position on the signal recorded were observed. This is the first study done by experimentation with the photoacoustic effect to show that standing waves have different amplitudes at different microphone positions.
{"title":"Detecting Photoacoustic Signals of Sulfur Hexafluoride at Varying Microphone Positions","authors":"Wittmann S. Murphy, Han Jung Park","doi":"10.4236/OJPC.2016.63005","DOIUrl":"https://doi.org/10.4236/OJPC.2016.63005","url":null,"abstract":"Photoacoustic spectroscopy was used to test the photoacoustic properties \u0000of sulfur hexafluoride, an optically thick and potent greenhouse gas. While \u0000exploring the photoacoustic effect of sulfur hexafluoride, the effects of the \u0000position of the microphone within a gas cell were determined. Using a 35 cm gas \u0000cell, microphones were positioned at 17.5 cm, the middle of the gas cell, 12.5 \u0000cm, 7.5 cm, and 2.5 cm from the window of the cell. From the photoacoustic \u0000signal produced for each resonance frequency at each microphone position, the effects \u0000of acoustic pressure produced at each position on the signal recorded were \u0000observed. This is the first study done by experimentation with the \u0000photoacoustic effect to show that standing waves have different amplitudes at \u0000different microphone positions.","PeriodicalId":59839,"journal":{"name":"物理化学期刊(英文)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70502762","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, yet no theory to unify conceptions. The present paper describes methods to derive bonds and charge location in double-face-centered cubic crystals with 4 and 6 atoms per unit cell using two novel rules introduced in earlier works: the even-odd and the isoelectronicity rules. Both of these rules were previously applied to ions, molecules and some solids, and the even-odd rule was also tested on two covalent crystal structures: centered-cubic and single-face-centered cubic crystals. In the present study, the diamond-like structure was subjected to the isoelectronicity rule in order to derive Zinc-blende structures. Rock-salt-like crystals were derived from each other using both rules. These structures represent together more than 230 different crystals. Findings for these structures are threefold: both rules describe a very sure method to obtain valid single covalent-bonded structures; single covalent structures can be used in every case instead of the classical ionic model; covalent bonds and charges positions do not have any relation with the valence number given in the periodic table.
{"title":"The Even-Odd and the Isoelectronicity Rules Applied to Single Covalent Bonds in Ionic, Double-Face-Centered Cubic and Diamond-Like Crystals","authors":"G. Auvert, M. Auvert","doi":"10.4236/OJPC.2016.62002","DOIUrl":"https://doi.org/10.4236/OJPC.2016.62002","url":null,"abstract":"Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, yet no theory to unify conceptions. The present paper describes methods to derive bonds and charge location in double-face-centered cubic crystals with 4 and 6 atoms per unit cell using two novel rules introduced in earlier works: the even-odd and the isoelectronicity rules. Both of these rules were previously applied to ions, molecules and some solids, and the even-odd rule was also tested on two covalent crystal structures: centered-cubic and single-face-centered cubic crystals. In the present study, the diamond-like structure was subjected to the isoelectronicity rule in order to derive Zinc-blende structures. Rock-salt-like crystals were derived from each other using both rules. These structures represent together more than 230 different crystals. Findings for these structures are threefold: both rules describe a very sure method to obtain valid single covalent-bonded structures; single covalent structures can be used in every case instead of the classical ionic model; covalent bonds and charges positions do not have any relation with the valence number given in the periodic table.","PeriodicalId":59839,"journal":{"name":"物理化学期刊(英文)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70502963","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
M. Afqir, A. Tachafine, D. Fasquelle, M. Elaatmani, J. Carru, A. Zegzouti, M. Daoud
This Ce-doped strontium bismuth tantalate SrBi1.8Ce0.2Ta2O9 was prepared by solid-state reaction. X-ray diffraction was used to determine the crystal structure of the powders. The Raman spectrum of SrBi1.8Ce0.2Ta2O9 sample was measured to confirm X-ray diffraction result. The microstructure of ceramic was observed by Scanning Electron Microscope (SEM). The Temperature dependence of the dielectric properties of ceramic was investigated from the room temperature to 400°C.
{"title":"Synthesis, Structural and Dielectric Properties of SrBi1.8Ce0.2Ta2O9","authors":"M. Afqir, A. Tachafine, D. Fasquelle, M. Elaatmani, J. Carru, A. Zegzouti, M. Daoud","doi":"10.4236/OJPC.2016.62004","DOIUrl":"https://doi.org/10.4236/OJPC.2016.62004","url":null,"abstract":"This Ce-doped strontium bismuth tantalate SrBi1.8Ce0.2Ta2O9 was prepared by solid-state reaction. X-ray diffraction was used to determine the crystal structure of the powders. The Raman spectrum of SrBi1.8Ce0.2Ta2O9 sample was measured to confirm X-ray diffraction result. The microstructure of ceramic was observed by Scanning Electron Microscope (SEM). The Temperature dependence of the dielectric properties of ceramic was investigated from the room temperature to 400°C.","PeriodicalId":59839,"journal":{"name":"物理化学期刊(英文)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70502715","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A. Belhadi, S. Boumaza, Amar Djadoun, M. Trari, O. Chérifi
The steam reforming of methane over NiO/ZnO mixed oxides with different nickel contents was studied. Solids to x% Ni/ZnO (x = 4 and 10%) were deposited on ZnO by impregnation from nickel nitrate solution; after vaporization the solid is calcined at 500°C for 6 h. The catalysts were characterized by X-ray diffraction (XRD) and BET method, scanning electron microscopy (SEM) and temperature programmed reduction (TPR). The XRD patterns revealed the NiO phase for all calcined catalysts. The chemical analysis confirmed the theoretical values of nickel. The catalysts were pre-treated under hydrogen at 500°C in situ, overnight before testing for the steam reforming of methane reaction (CH4/H2O/Ar = 10/10/80) in the temperature range (475°C - 650°C) under atmospheric pressure. The activities of both catalysts were investigated in a fixed-bed reactor for the Methane Steam Reforming (MSR) reaction. Globally, it was shown that the catalyst 10% nickel content has an important effect on the catalytic performances of solids i.e. the better results of hydrogen production were obtained with 10% wt. Ni/ZnO (28 ′ 10-3 mol/g catalyst).
{"title":"Methane Steam Reforming on Supported Nickel, Effect of Nickel Content for Product Hydrogen","authors":"A. Belhadi, S. Boumaza, Amar Djadoun, M. Trari, O. Chérifi","doi":"10.4236/OJPC.2016.62003","DOIUrl":"https://doi.org/10.4236/OJPC.2016.62003","url":null,"abstract":"The steam reforming of methane over NiO/ZnO mixed oxides with different nickel contents was studied. Solids to x% Ni/ZnO (x = 4 and 10%) were deposited on ZnO by impregnation from nickel nitrate solution; after vaporization the solid is calcined at 500°C for 6 h. The catalysts were characterized by X-ray diffraction (XRD) and BET method, scanning electron microscopy (SEM) and temperature programmed reduction (TPR). The XRD patterns revealed the NiO phase for all calcined catalysts. The chemical analysis confirmed the theoretical values of nickel. The catalysts were pre-treated under hydrogen at 500°C in situ, overnight before testing for the steam reforming of methane reaction (CH4/H2O/Ar = 10/10/80) in the temperature range (475°C - 650°C) under atmospheric pressure. The activities of both catalysts were investigated in a fixed-bed reactor for the Methane Steam Reforming (MSR) reaction. Globally, it was shown that the catalyst 10% nickel content has an important effect on the catalytic performances of solids i.e. the better results of hydrogen production were obtained with 10% wt. Ni/ZnO (28 ′ 10-3 mol/g catalyst).","PeriodicalId":59839,"journal":{"name":"物理化学期刊(英文)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70502660","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An attempt has been made to analyze the effect of surface site on the spin state for the interaction of NO with Pd2, Rh2 and PdRh nanoparticles that supported at regular and defective MgO(001) surfaces. The adsorption properties of NO on homonuclear, Pd2, Rh2, and heteronuclear transition metal dimers, PdRh, that deposited on MgO(001) surface have been studied by means of hybrid density functional theory calculations and embedded cluster model. The most stable NO chemisorption geometry is in a bridge position on Pd2 and a top configuration of Rh2 and PdRh with N-down oriented. NO prefers binding to Rh site when both Rh and Pd atoms co-exist in the PdRh. The natural bond orbital analysis (NBO) reveals that the electronic structure of the adsorbed metal represents a qualitative change with respect to that of the free metal. The adsorption properties of NO have been analyzed with reference to the NBO, charge transfer, band gaps, pairwise and non-pairwise additivity. The binding of NO precursor is dominated by the E(i)Mx-NO pairwise additive components and the role of the support was not restricted to supporting the metal. The adsorbed dimers on the MgO surface lose most of the metal-metal interaction due to the relatively strong bond with the substrate. Spin polarized calculations were performed and the results concern the systems in their more stable spin states. Spin quenching occurs for Rh atom, Pd2, Rh2 and PdRh complexes at the terrace and defective surfaces. The adsorption energies of the low spin states of spin quenched complexes are always greater than those of the high spin states. The metal-support and dimer-support interactions stabilize the low spin states of the adsorbed metals with respect to the isolated metals and dimers. Although the interaction of Pd, Rh, Pd2, Rh2 and PdRh particles with Fs sites is much stronger than the regular sites O2-, the adsorption of NO is stronger when the particular dimers are supported on an anionic site than on an Fs site of the MgO(001). The encountered variations in magnetic properties of the adsorbed species at MgO(001) surface are correlated with the energy gaps of the frontier orbitals. The results show that the spin state of adsorbed metal atoms on oxide supports and the role of precursor molecules on the magnetic and binding properties of complexes need to be explicitly taken into account.
{"title":"Effect of Surface Site on the Spin State for the Interaction of NO with Pd 2 , Rh 2 and PdRh Nanoparticles Supported at Regular and Defective MgO(001) Surfaces","authors":"S. Aal","doi":"10.4236/OJPC.2016.61001","DOIUrl":"https://doi.org/10.4236/OJPC.2016.61001","url":null,"abstract":"An attempt has been made to analyze the effect of surface site on the spin state for the interaction of NO with Pd2, Rh2 and PdRh nanoparticles that supported at regular and defective MgO(001) surfaces. The adsorption properties of NO on homonuclear, Pd2, Rh2, and heteronuclear transition metal dimers, PdRh, that deposited on MgO(001) surface have been studied by means of hybrid density functional theory calculations and embedded cluster model. The most stable NO chemisorption geometry is in a bridge position on Pd2 and a top configuration of Rh2 and PdRh with N-down oriented. NO prefers binding to Rh site when both Rh and Pd atoms co-exist in the PdRh. The natural bond orbital analysis (NBO) reveals that the electronic structure of the adsorbed metal represents a qualitative change with respect to that of the free metal. The adsorption properties of NO have been analyzed with reference to the NBO, charge transfer, band gaps, pairwise and non-pairwise additivity. The binding of NO precursor is dominated by the E(i)Mx-NO pairwise additive components and the role of the support was not restricted to supporting the metal. The adsorbed dimers on the MgO surface lose most of the metal-metal interaction due to the relatively strong bond with the substrate. Spin polarized calculations were performed and the results concern the systems in their more stable spin states. Spin quenching occurs for Rh atom, Pd2, Rh2 and PdRh complexes at the terrace and defective surfaces. The adsorption energies of the low spin states of spin quenched complexes are always greater than those of the high spin states. The metal-support and dimer-support interactions stabilize the low spin states of the adsorbed metals with respect to the isolated metals and dimers. Although the interaction of Pd, Rh, Pd2, Rh2 and PdRh particles with Fs sites is much stronger than the regular sites O2-, the adsorption of NO is stronger when the particular dimers are supported on an anionic site than on an Fs site of the MgO(001). The encountered variations in magnetic properties of the adsorbed species at MgO(001) surface are correlated with the energy gaps of the frontier orbitals. The results show that the spin state of adsorbed metal atoms on oxide supports and the role of precursor molecules on the magnetic and binding properties of complexes need to be explicitly taken into account.","PeriodicalId":59839,"journal":{"name":"物理化学期刊(英文)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"70502748","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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